CN111117695A

CN111117695A - Method for processing inferior heavy oil

Info

Publication number: CN111117695A
Application number: CN201811285592.0A
Authority: CN
Inventors: 李子锋; 张书红; 李延军; 任磊; 申海平
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2018-10-31
Filing date: 2018-10-31
Publication date: 2020-05-08
Anticipated expiration: 2038-10-31
Also published as: CN111117695B

Abstract

The invention relates to the field of heavy oil processing, and discloses a method for processing inferior heavy oil, which comprises the following steps: (1) introducing the inferior heavy oil and the cracking contact agent into a contact cracking unit for contact cracking reaction to obtain a carbon-containing contact agent; (2) introducing a carbon-containing contact agent into a gasification unit for gasification reaction to obtain a metal-loaded regenerative contact agent and synthesis gas; (3) recycling at least part of the regenerated contact agent to the step (1) to participate in the contact cracking reaction; controlling the circulating amount of the regenerated contact agent in the step (3) and the conditions of the contact cracking reaction to ensure that the Ni/V weight ratio on the cracking contact balancing agent in the step (1) is more than or equal to 1.8. The inferior heavy oil containing metallic nickel contacts with the contact agent in the contact cracking-coke gasification process, so that the contact agent is loaded with quantitative metallic nickel and is applied to coke gasification reaction, and the purpose of producing more carbon monoxide and hydrogen can be realized.

Description

Method for processing inferior heavy oil

Technical Field

The invention relates to the field of heavy oil processing, in particular to a method for processing inferior heavy oil.

Background

At present, the deterioration degree and the heaviness degree of petroleum resources are increasingly deepened, and the characteristics of high sulfur, high carbon residue, high metal and the like of petroleum raw materials provide new challenges for oil refining technology.

At present, when heavy and poor raw oil is processed by catalytic cracking, the catalytic cracking process and the catalyst present challenges. The non-catalytic processing technology of inferior heavy oil mainly comprises delayed coking, fluid coking, flexible coking and the like. But the coking process has the problems of high coke yield and difficult utilization of low-quality coke. The delayed coking process can generate a large amount of petroleum coke with low added value, and the yield of the petroleum coke is about 1.5 times of that of the Conradson carbon residue, so that the petroleum resource cannot be efficiently utilized.

The technology is developed for adapting the situation, and the technology transfers high carbon residue and high metal in the inferior heavy oil to the contact agent by a cracking reaction in the presence of the contact agent, and then converts the coke into rich in CO and H by a gasification reaction₂Syngas, a technology that reduces coke yield compared to delayed coking and achieves in situ conversion of the coke. Solves the problem that the high-sulfur petroleum coke is not environment-friendly. Because the carbon residue of the processing raw material is high, the process aims to process inferior heavy oil in an environment-friendly way, convert petroleum coke into heat in situ, and provide steam, heat and the like for refineries.

Generally, the reaction temperature (about 1000 ℃) is high for the coke-to-syngas reaction, and for a contact agent with certain catalytic activity, the activity and structure of the contact agent are greatly damaged under high-temperature hydrothermal conditions, so that the reaction temperature of the coke gasification unit needs to be reduced. And the alkali metal and the alkaline earth metal have catalytic gasification reaction activity and can reduce the coke gasification reaction temperature.

CN101757903A discloses an alkali metal and alkaline earth metal containing catalyst with cracking and gasification functions, which contains 35-60% of pseudo-boehmite, 2-10% of alumina sol, 20-49.5% of kaolin, and 5-30% of alkali metal and alkaline earth metal calculated by oxides.

CN101898143A discloses an inferior heavy oil cracking gasification catalyst, which comprises a carrier, a binder, a gasification active component and a cracking active component, wherein the gasification active component is alkali metal and alkaline earth metal, the content of oxide is 2-30% by taking the total amount of the catalyst as a reference, and the cracking active component is a shape-selective molecular sieve with the silicon-aluminum ratio of 20-200.

However, since both alkali metals and alkaline earth metals are alkaline, they have an influence on the cracking activity of the contact agent, and the loss in hydrothermal environment is also severe, so that the production cost is significantly increased.

Therefore, there is a need in the art to find a new method for processing heavy oil to achieve the goal of producing more carbon monoxide and hydrogen at a lower cost and in an environmentally friendly manner.

Disclosure of Invention

The invention aims to provide a novel method for processing inferior heavy oil so as to realize the high yield of carbon monoxide and hydrogen with low cost and environmental protection.

In order to achieve the above object, the present invention provides a method for processing inferior heavy oil, comprising:

(1) introducing inferior heavy oil and a cracking contact agent into a contact cracking unit for contact cracking reaction, and separating reaction effluent to obtain a gasoline fraction, a diesel oil fraction, a wax oil fraction and a carbon-containing contact agent, wherein the residual carbon content of the inferior heavy oil is 30-50 wt%, the total metal content is 25-1000 mug/g, the Ni content in the inferior heavy oil is 15-900 mug/g, and the V content is less than or equal to 150 mug/g;

(2) introducing the carbon-containing contact agent into a gasification unit to contact with a gasification agent to carry out gasification reaction to obtain a regenerated contact agent loaded with metal and a catalyst containing CO and H₂The synthesis gas of (2);

(3) recycling at least a portion of said regenerated contact agent back to step (1) to participate in said contact cracking reaction;

wherein, the circulation amount of the regenerated contact agent in the step (3) and the conditions of the contact cracking reaction are controlled, so that the Ni/V weight ratio on the cracking contact balancing agent in the step (1) is more than or equal to 1.8; the cracking contact balancer is a mixture of fresh cracking contact agent and regenerated contact agent recycled in the step (3).

The method provided by the invention can realize the high yield of carbon monoxide and hydrogen by utilizing the metal nickel contained in the inferior heavy oil, and particularly, the inferior heavy oil containing the metal nickel is contacted with a contact agent in the contact cracking-coke gasification process, so that the contact agent is loaded with a certain amount of metal nickel and applied to the coke gasification reaction, and the purpose of high yield of carbon monoxide and hydrogen can be realized.

Further, the method provided by the present inventors is capable of significantly reducing production costs compared to methods provided by the prior art.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

As previously mentioned, the present invention provides a method of processing heavy oil of poor quality, the method comprising:

(2) introducing the carbon-containing contact agent into a gasification unit to contact with a gasification agent to carry out gasification reaction to obtain metal-loadedRegenerated contact agent and catalyst containing CO and H₂The synthesis gas of (2);

In particular, in the present invention, the Ni/V weight ratio on the cracking contact balancer is 1.8 or more, which represents the weight ratio between Ni and V having a catalytic function on the cracking contact balancer. For example, when the cracking contact balancer contains V in a passivated state (e.g., V forms a complex metal compound having no catalytic function with other metals), V in the passivated state is not included in the aforementioned Ni/V weight ratio ≧ 1.8, and likewise, Ni in the passivated state is not included in the aforementioned Ni/V weight ratio ≧ 1.8.

In the invention, the cracking contact agent refers to a catalyst for carrying out contact cracking reaction, and the cracking contact agent is fresh cracking contact agent when the reaction just starts to be carried out; after the reaction is carried out for a certain time, the cracking contact agent is a mixture of fresh cracking contact agent and regenerated contact agent recycled from the step (3), namely the cracking contact balancing agent.

In order to further increase the carbon monoxide yield, the circulating amount of the regeneration contact agent in the step (3) is preferably controlled so that the average Ni content on the cracking contact balancing agent in the step (1) is 0.2 to 4.0 wt%, and more preferably the average Ni content is 1.5 to 3.0 wt%.

In the present invention, in step (1), the volume ratio of the fresh cracking contact agent and the regenerated contact agent is preferably adjusted to achieve an average Ni content on the cracking contact agent in step (1) of 0.2 to 4.0 wt%, preferably 1.5 to 3.0 wt%.

According to a preferred embodiment, said cracking contact agent has an average particle size of from 20 to up to100 μm, a specific surface area of 50-200 m²The pore volume is 0.1-0.4 mL/g; more preferably, the average particle size of the cracking contact agent is 40-85 μm, and the specific surface area is 60-150 m²The pore volume is 0.1-0.4 mL/g.

According to a preferred embodiment, the Ni/V weight ratio in the low-grade heavy oil is greater than or equal to 1.8. When the weight ratio of Ni/V in the inferior heavy oil is more than or equal to 1.8, the weight ratio of Ni/V on the cracking contact balancing agent in the method is basically the same as that in the inferior heavy oil.

According to another preferred embodiment, the Ni/V weight ratio in the low-grade heavy oil is less than 1.8, and the contact cracking reaction is carried out in the presence of a vanadium trap, wherein the vanadium trap is used in an amount such that the Ni/V weight ratio on the cracking contact balancer in the step (1) is more than or equal to 1.8.

According to a further preferred embodiment, the content of metallic vanadium in the low-grade heavy oil is more than or equal to 30 mu g/g, and the contact cracking reaction is carried out in the presence of a vanadium trap, wherein the vanadium trap is used in an amount such that the Ni/V weight ratio on the cracking contact balancer in the step (1) is more than or equal to 1.8.

The vanadium trap of the present invention may be present on the cracking contact agent.

The invention has no special requirement on the type of the vanadium trap, can be various vanadium traps which are conventionally used in the field, and a person skilled in the art can determine the proper dosage of the vanadium trap according to the content of the metal vanadium in the inferior heavy oil. The vanadium trap can be at least one of the metal traps disclosed in CN103789014A, for example.

When the nickel content in the inferior heavy oil is too high, the contact cracking reaction of the present invention may be performed in the presence of a nickel passivator. Preferably, the nickel-passivating agent is at least one of Sb-containing nickel-passivating agents. The dosage of the nickel passivation agent is such that the Sb/Ni atomic ratio in the materials for the contact cracking reaction is 0.5-1.0.

Preferably, the content of the silicon-aluminum material in the cracking contact agent is 30-90 wt% based on the total weight of the cracking contact agent.

Preferably, the silica-alumina material is selected from at least one of clay, kaolin, montmorillonite, rectorite, illite, chlorite, pseudoboehmite, and silica.

According to a particularly preferred embodiment, the silica-alumina material is a mixture of kaolin and pseudo-boehmite, and the weight ratio of kaolin to pseudo-boehmite in the mixture is 1: (0.01 to 100); more preferably, the weight ratio of kaolin to pseudo-boehmite in the mixture is 1: (0.05-20).

Preferably, the silicon-aluminum material contains a mesoporous silicon-aluminum material, the mesoporous silicon-aluminum material has a pseudo-boehmite crystal phase structure, and the specific surface area of the mesoporous silicon-aluminum material is 200-400 m²(iv)/g, pore volume of 0.5 to 2.0mL/g, and average pore diameter of 8 to 20 nm. More preferably, the average pore diameter of the mesoporous silicon-aluminum material is 10-20 nm.

Preferably, the cracking contact agent also contains a binder.

Preferably, the binder is provided by an aluminium sol and/or a silica sol.

In the invention, the content of the mesoporous silicon-aluminum material is 0-40 wt% based on the total weight of the cracking contact agent.

The method for preparing the cracking contact agent used in the invention comprises the following steps, but is not limited to the following steps: pulping the silicon-aluminum material, and adjusting the pH of the pulp by using inorganic acid to obtain pulp; adding a binder, uniformly mixing, spray-drying, washing, filtering, drying, and roasting at 500-800 ℃.

Preferably, the conditions of the contact cracking reaction include: the reaction temperature is 450-600 ℃, and the weight hourly space velocity is 1-100 h^-1The weight ratio (agent-oil ratio) of the cracking contact agent to the inferior heavy oil is (1-20): 1, the weight ratio of the water vapor to the inferior heavy oil (water-oil ratio) is (0.1-0.5): 1, the reaction pressure is 0.1-1.0 MPa.

Preferably, the gasifying agent is steam or a mixture of steam and oxygen.

Preferably, the temperature of the gasification reaction is 650-950 ℃.

Preferably, the low-grade heavy oil is selected from at least one of crude oil, acid-containing crude oil, ultra-heavy oil, atmospheric residue, vacuum gas oil, coker gas oil, deasphalted oil, oil sand bitumen, hydrocracked tail oil, coal tar, shale oil, tank bottom oil and coal liquefaction residue.

Compared with the prior art, the cracking contact agent with specific content of metallic nickel formed by using metallic Ni in inferior heavy oil can realize the production of more effective gases of carbon monoxide and hydrogen, reduce the production cost of the cracking contact agent and overcome the defect that additional metal is lost in cracked products.

Meanwhile, the method for processing the inferior heavy oil provided by the invention can also ensure that the yield of high value-added cracking products in the contact cracking unit is higher.

The present invention will be described in detail below by way of examples. In the following examples, various raw materials used are commercially available ones unless otherwise specified.

To demonstrate the beneficial effects of the methods provided by the present invention under laboratory conditions, the regenerated contact agents described herein were prepared by the methods of the preparative examples for use in the methods of the examples.

The specific surface area and pore volume of the cracking contact agent in table 1 were analyzed by the low temperature nitrogen adsorption volumetric method, and the metal mass fraction was analyzed by the XRF (X-ray fluorescence spectroscopy) method. The basis for the amounts of material in table 1 is the total weight of the cracking contact agent. In Table 1, when the V content is 0, it means that the Ni/V weight ratio is positive and infinitely large.

The following contact agent A-0 also contains: 30 wt% of a mesoporous silicon aluminum material based on the total weight of the contact agent A-0, wherein the mesoporous silicon aluminum material is CN102079986A, the mesoporous silicon aluminum material SA-1 used in example 1; kaolin particle of 60 wt% and alumina sol of 10 wt% are added, and the mixture is spray dried and calcined at 600 deg.c.

Preparation example 1

The contact agent A-0 with the properties shown in the table 1 is taken as a cracking contact agent for experiments, nickel naphthenate (produced by Fuho synthetic materials) or vanadium naphthenate (produced by Fuho synthetic materials) is taken as a metal pollution source of the contact agent, diesel oil is taken as a diluent, the metal pollution is carried out on the contact agent by using a saturated impregnation method, the drying is carried out for 2h at 200 ℃, the roasting is carried out for 4h at 500 ℃, and then the hydrothermal aging treatment is carried out for 17h at 750 ℃ in 100 percent of steam, so as to obtain the cracking contact agent containing the metal, which is numbered from A-1 to A-5, and related parameters are shown in the table 1.

Preparation example 2

A contact agent A-0 with the properties shown in the table 1 is used as a cracking contact agent for experiments, 210g of the contact agent is loaded on a fixed fluidized bed experimental device for contact agent cracking experiments, the used raw oil is a mixture of deasphalted oil and slurry oil, the properties of the raw material are shown in the table 2, and the experimental conditions comprise: the reaction temperature is 500 ℃, and the weight hourly space velocity is 4h^-1The agent-oil ratio is 7.0, the water-oil ratio is 0.23, 18kg of raw oil is accumulated to obtain the simulated industrial balancing agent A-6, and relevant parameters are shown in table 1.

TABLE 1

Sample numbering	A-0	A-1	A-2	A-3	A-4	A-5	A-6
								Nickel/weight%	0	1.52	1.58	2.51	3.13	0.54	1.05
Vanadium per weight%	0	0	1.0	1.01	0	0	0.51
								Nickel/vanadium weight ratio	-	-	1.58	2.50	-	-	2.1
Vanadium catching agent/weight%	0	0	0	10	0	0	0
								Specific surface area/(m)²/g)	100	99	98	70	91	100	99
Pore volume/(ml/g)	0.26	0.25	0.24	0.21	0.23	0.26	0.25
								Average particle diameter/. mu.m	65	65	65	65	65	65	64

The vanadium trap in table 1 was CN103789014A and the metal trap a1 prepared in example 1.

Example 1

A fixed fluidized bed experimental apparatus was loaded with 210g of the cracking contact agent (except for the sample numbered A-2) in Table 1 to perform a contact agent cracking experiment, the raw oil used was a mixture of deasphalted oil and slurry oil, the raw material properties are shown in Table 2, and the experimental conditions include: the reaction temperature is 500 ℃, and the weight hourly space velocity is 4h^-1The agent-oil ratio is 7.0, and the water-oil ratio is 0.23. Under the same reaction conditions, carbon-containing contact agents of C-A0, C-A1, C-A3, C-A4, C-A5 and C-A6 are respectively obtained. Coke gasification experiment of carbon-containing contact agent in tubular fixed fluidized bedThe process is carried out, the material of the reactor is quartz, so as to eliminate the influence of the metal of the reactor on the experimental result, the gasification reaction temperature is 710 ℃, the gasification agent is water vapor (80 vol%), oxygen (20 vol%), and the linear velocity of the gasification agent is 0.1m/s, and the experimental result is shown in Table 3.

Comparative example 1

The same procedure was followed as in example 1, except that the cracking contact agent was A-2 in Table 1 and the resulting char-containing contact agent was C-A2. The results are shown in Table 3.

TABLE 2

TABLE 3

Example 2

This example was carried out in a similar manner to example 1, except that the experimental conditions for the contact cracking reaction of this example included: the reaction temperature is 550 ℃, and the weight hourly space velocity is 6h^-1The agent-oil ratio is 8.5, and the water-oil ratio is 0.23.

The temperature of the gasification reaction is 790 ℃, and the gasifying agent is steam.

The rest of the process was the same as in example 2, and as a result, synthesis gas (H) obtained in this example was obtained₂And CO) with CO₂The volume ratio of (a) is shown in table 4.

Comparative example 2

The same procedure was followed as in example 2, except that the cracking contact agent was A-2 in Table 1 and the resulting char-containing contact agent was C-A2. The results are shown in Table 4.

TABLE 4

Cracking contact numbering	A-0	A-1	A-2	A-3	A-4	A-5	A-6
								n(CO+H₂)/n(CO₂)	2.05	2.41	1.99	2.31	2.49	2.25	2.21

As can be seen from the results of tables 3 and 4, the process for processing inferior heavy oil provided by the present invention can achieve the object of producing more effective gases of carbon monoxide and hydrogen when controlling the Ni/V weight ratio on the cracking contact balancer to be 1.8 or more, relative to comparative examples 1 and 2 (contact agent A-2).

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims

1. A method of processing low grade heavy oil, the method comprising:

2. A process of processing heavy oil of poor quality as claimed in claim 1, wherein the circulation amount of said regenerated contact agent in step (3) and the conditions of said contact cracking reaction are controlled so that the average Ni content on said cracking contact balancer in step (1) is 0.2-4.0 wt%, preferably 1.5-3.0 wt%.

3. The method for processing inferior heavy oil according to claim 1 or 2, wherein the average particle diameter of the cracking contact agent is 20 to 100 μm, and the specific surface area is 50 to 200m²The pore volume is 0.1-0.4 mL/g.

4. A method of processing heavy oil of poor quality as claimed in claim 1 or claim 2, wherein the cracking contact agent has an average particle size of 40 to 85 μm and a specific surface areaThe product is 60 to 150m²The pore volume is 0.15-0.35 mL/g.

5. A method of processing heavy oil of poor quality according to any of claims 1 to 4 wherein the Ni/V weight ratio in the heavy oil of poor quality is not less than 1.8.

6. A process of processing low quality heavy oil according to any one of claims 1 to 4 wherein the Ni/V weight ratio in the low quality heavy oil is < 1.8 and the contact cracking reaction is carried out in the presence of a vanadium trap used in such an amount that the Ni/V weight ratio on the cracking contact balancer in step (1) is > 1.8.

7. A process of processing low quality heavy oil according to any one of claims 1 to 4, wherein the content of metallic vanadium in the low quality heavy oil is not less than 30 μ g/g, and the contact cracking reaction is carried out in the presence of a vanadium trap in an amount such that the Ni/V weight ratio on the cracking contact balancer in step (1) is not less than 1.8.

8. The method of processing inferior heavy oil according to any one of claims 1 to 7, wherein the content of the silicon-aluminum material in the cracking contact agent is 30 to 90 wt% based on the total weight of the cracking contact agent.

9. The method of processing low grade heavy oil of claim 8, wherein the silica-alumina material is selected from at least one of clay, kaolin, montmorillonite, rectorite, illite, chlorite, pseudoboehmite, and silica.

10. The method of claim 9 wherein the silica-alumina material is a mixture of kaolin and pseudoboehmite, and wherein the kaolin and pseudoboehmite are present in a weight ratio of 1: (0.01 to 100); preferably, the first and second electrodes are formed of a metal,

in the mixture, the weight ratio of kaolin to pseudo-boehmite is 1: (0.05-20).

11. The method for processing the inferior heavy oil according to claim 9, wherein the silicon-aluminum material contains a mesoporous silicon-aluminum material, the mesoporous silicon-aluminum material has a pseudo-boehmite crystal phase structure, and the specific surface area of the mesoporous silicon-aluminum material is 200-400 m²(iv)/g, pore volume of 0.5 to 2.0mL/g, and average pore diameter of 8 to 20 nm.

12. A method of processing heavy oil of poor quality according to any of claims 9 to 11 wherein the cracking contact agent further comprises a binder.

13. A method of processing low quality heavy oil according to any one of claims 1 to 8 wherein the conditions of the contact cracking reaction comprise: the reaction temperature is 450-600 ℃, and the weight hourly space velocity is 1-100 h^-1The weight ratio of the cracking contact agent to the inferior heavy oil is (1-20): 1, the weight ratio of the water vapor to the inferior heavy oil is (0.1-0.5): 1, the reaction pressure is 0.1-1.0 MPa.

14. The method of any one of claims 1 to 8 wherein the gasifying agent is steam or a mixture of steam and oxygen; preferably, the first and second electrodes are formed of a metal,

the temperature of the gasification reaction is 650-950 ℃.

15. The method of processing heavy oil of any of claims 1-8, wherein the heavy oil of poor quality is selected from at least one of crude oil, acid-containing crude oil, ultra-heavy oil, atmospheric residue, vacuum gas oil, coker gas oil, deasphalted oil, oil sand bitumen, hydrocracked tail oil, coal tar, shale oil, tank bottom oil, and coal liquefaction residue oil.